AbstractThree-dimensional (3D) topological insulators are a new state of quantum matter, which exhibits both a bulk band structure with an insulating energy gap as well as metallic spin-polarized Dirac fermion states when interfaced with a topologically trivial material. There have been various attempts to tune the Dirac point to a desired energetic position for exploring its unusual quantum properties. Here we show a direct experimental proof by angle-resolved photoemission of the realization of a vertical topological p–n junction made of a heterostructure of two different binary 3D TI materials Bi₂Te₃ and Sb₂Te₃ epitaxially grown on Si(111). We demonstrate that the chemical potential is tunable by about 200 meV when decreasing the upper Sb₂Te₃ layer thickness from 25 to 6 quintuple layers without applying any external bias. These results make it realistic to observe the topological exciton condensate and pave the way for exploring other exotic quantum phenomena in the near future.